CN111468138B - One-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light catalyst and preparation method and application thereof - Google Patents
One-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light catalyst and preparation method and application thereof Download PDFInfo
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
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Abstract
The invention belongs to the technical field of catalysis, and particularly relates to one-dimensional rod-shaped CuBi2O4@CuBi2S4The visible light catalyst and the preparation method and the application thereof are as follows: mixing Na2S is dissolved in water, CuBi is added2O4Stirring, transferring to an autoclave for reaction, cooling to room temperature, collecting a sample, washing and drying to obtain a target product. One-dimensional rod-shaped CuBi2O4@CuBi2S4Within 180min, catalytically synthesizing H2O2The yield reaches 201.9 mu mol/L. The method has the characteristics of simplicity, convenience, high efficiency, low cost and high visible light absorption degree, and can be applied to the fields of photocatalytic preparation of hydrogen peroxide, degradation of organic matters and the like.
Description
Technical Field
The invention relates to a visible light response one-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light photocatalyst, preparation method thereof and method for preparing H through photocatalysis2O2The application of the aspect is mainly aimed at industrial large-scale production of H2O2Belonging to the technical field of production of high value-added chemicals and catalysts.
Background
The photocatalysis technology is a mature green technology which has low cost and high performance and can not cause secondary pollution, has potential application prospect in the aspects of green oxidative degradation and green synthesis, has obvious removal effect on pollutants seriously threatening the health of human beings in the natural environment, relieves the problem of insufficient energy demand, and has been generally concerned by researchers at home and abroad.
Hydrogen peroxide (H)2O2) Is the most important 100 chemicals in the worldOne of the substances is an eco-friendly energy carrier, an oxidant and an environmental remediation agent. Conventional H2O2The industrial synthesis methods of (a) have limited practical applications due to the complex processes, high costs and the production of large amounts of waste toxic by-products. In recent years, photocatalytic production of H2O2The method has received more and more attention from people because the process only needs water, oxygen and sunshine as raw materials, converts low-density solar energy into storable chemical energy, and has the advantages of no secondary pollution, simple equipment, less investment, high yield and the like. In this solar-fueled process, the catalyst, driven by the sun's light, produces photoexcited electrons that reduce oxygen and produce H2O2This can be accomplished by a multi-step single electron or one-step dual electron type process. In early attempts, inorganic semiconductor photocatalysts have been widely used for producing H2O2E.g. TiO2Systems, usually by being at O2Carrying out O on a conduction band under the irradiation of ultraviolet light in saturated water2Reduction to form H2O2. Photo-generated electron promoted O2Reduction of two electrons and generation of H2O2. However, due to TiO2To H2O2Is low and in the course of the photocatalytic reaction, H is produced2O2Irradiated ultraviolet ray (lambda)<400nm) and thus the production efficiency is very low. In addition, the recombination of photogenerated electrons and electron holes results in low photon yield, and the practical application of the photoelectrocatalysis technology is limited.
CuBi2O4Is a spinel semiconductor due to CuBi2O4The dielectric property and the optical property of the material are good, the thermal stability is good, especially the absorption property in the visible light region is excellent, the material is widely applied to various fields, and the material is also a very good photocathode material. But due to its narrow band gap, photogeneration e-And h+Are easily complexed and are therefore in H2O2Photocatalytic production is rarely reported. To reduce the chance of recombination, building heterostructures is a very efficient method.
Disclosure of Invention
One of the purposes of the invention is to provide one-dimensional rod-shaped CuBi with visible light response and capable of improving photo-generated electrons and photo-generated holes2O4@CuBi2S4Visible light catalyst and its preparation method.
Another object of the present invention is to provide a method for producing CuBi in one-dimensional rod shape2O4@CuBi2S4Preparation of H by catalysis of visible light catalyst2O2The method of (1).
In order to achieve the purpose, the invention adopts the technical scheme that: one-dimensional rod-shaped CuBi2O4@CuBi2S4The preparation method of the visible light catalyst comprises the following steps: mixing Na2S is dissolved in water, CuBi is added2O4Stirring, transferring to an autoclave for reaction, cooling to room temperature, collecting a sample, washing and drying to obtain a target product.
Preferably, the one-dimensional rod-shaped CuBi is2O4@CuBi2S4The visible light catalyst is characterized in that CuBi is added according to the mass ratio2O4:Na2S is 5: 6.
preferably, the one-dimensional rod-shaped CuBi is2O4@CuBi2S4The visible light photocatalyst is characterized in that the reaction is carried out by heating at 120 ℃ for 4 h.
Preferably, the one-dimensional rod-shaped CuBi is2O4@CuBi2S4The visible light catalyst is characterized in that the CuBi2O4The preparation method comprises the following steps: separately taking Bi (NO)3)3·5H2O、Cu(NO3)2·3H2Adding O and NaOH into deionized water, stirring, transferring into an autoclave for reaction, cooling to room temperature, collecting a sample, washing and drying to obtain CuBi2O4。
Preferably, the one-dimensional rod-shaped CuBi is2O4@CuBi2S4The visible light catalyst is characterized by massQuantitative ratio of Bi (NO)3)3·5H2O:Cu(NO3)2·3H2O:NaOH=242:60:87。
Preferably, the one-dimensional rod-shaped CuBi is2O4@CuBi2S4The visible light photocatalyst is characterized in that the reaction is carried out by heating at 180 ℃ for 24 h.
The one-dimensional rod-shaped CuBi2O4@CuBi2S4The application of visible light catalyst in preparing hydrogen peroxide by photocatalysis.
Preferably, the above application, method is as follows: mixing the one-dimensional rod-shaped CuBi2O4@CuBi2S4Adding visible light catalyst into deionized water, performing ultrasonic treatment for 10min, adjusting pH to acidity, and adding O2Introducing into the suspension, bubbling in the solution continuously and uniformly, magnetically stirring in dark for 60min to reach adsorption-desorption equilibrium before irradiation, and irradiating with light source for reaction.
Preferably, for the above applications, the pH is adjusted by HClO4The pH of the suspension was adjusted to 3.
Preferably, in the application, a 300W xenon lamp is used as a light source for illumination, and the lambda of the xenon lamp is more than or equal to 420 nm.
The invention has the beneficial effects that: the invention uses CuBi2O4And CuBi2S4The two materials are compounded, so that the photoresponse range and the photocatalytic performance are further improved, the efficiency of capturing photons is improved, the recombination of electron hole pairs is inhibited, the utilization rate of transition of electrons from a valence band to a conduction band is improved, and the photocatalytic activity is improved. With the process of the present invention, there is a high hydrogen peroxide (H) without any carbon emissions or pollutants and any co-catalyst involved2O2) Yield, within 180min, H2O2The yield reaches 201.9 mu mol/L, for producing H2O2Provides a green synthetic route and sustainable technology.
The invention has the advantages of simplicity, convenience, high efficiency, low cost and visible light absorptionHigh degree, the prepared one-dimensional rod-shaped CuBi2O4@CuBi2S4The catalytic material has the characteristics of narrow band gap, large specific surface area and high catalytic activity, has good visible light absorption performance and stability, high photoinduced charge transfer efficiency and good effect of preparing hydrogen peroxide by photocatalysis, and can be applied to the fields of preparing hydrogen peroxide by photocatalysis, degrading organic matters and the like.
Drawings
FIG. 1 is a one-dimensional rod-like CuBi2O4@CuBi2S4SEM image of catalyst, wherein a is a full view, b is detail enlargement
FIG. 2 is CuBi2O4、CuBi2O4@CuBi2S4-1、CuBi2O4@CuBi2S4-2 and CuBi2O4@CuBi2S4-XRD pattern of 3.
FIG. 3 is a graph of different gas environments vs. H2O2The resulting effect.
FIG. 4 is the different pH vs. H2O2The resulting effect.
FIG. 5 is a graph of CuBi under visible light irradiation2O4、CuBi2O4@CuBi2S4-1、CuBi2O4@CuBi2S4-2、 CuBi2O4@CuBi2S4-3 and CuBi2S4Generation of H2O2And (4) concentration.
Detailed Description
EXAMPLE 1 one-dimensional rod-like CuBi2O4@CuBi2S4Preparation of visible light catalyst
One-dimensional rod-like CuBi2O4Preparation of
2.42g of Bi (NO) were weighed respectively3)3 .5H2O、0.6g Cu(NO3)3·3H2O and 0.87g NaOH were added to 80mL of deionized water and stirred for 3 h. The precursor solution was then transferred to a stainless steel autoclave with a teflon liner and heated at 180 ℃ for 24 h.Cooling to room temperature, collecting the product, washing with deionized water for several times, and drying in an oven at 70 deg.C for 8 hr to obtain CuBi2O4。
(II) one-dimensional rod-like CuBi2O4@CuBi2S4Preparation of visible light catalyst
0.3g of Na was weighed2S is dissolved in 35mL of deionized water, and 0.25g of CuBi is added2O4Stirring for 30min, transferring into an autoclave for reaction, and heating at 120 ℃ for 4 h. Cooling to room temperature, collecting the sample, washing with deionized water for several times, and drying in an oven at 70 ℃ for 8h to obtain CuBi2O4@CuBi2S4A composite material.
0.1g, 0.3g, 0.5g and 2g (excess) of Na were added to the mixture, respectively2S is dissolved in 35mL of deionized water, and 0.25g of CuBi is added2O4Stirring for 30min, transferring into an autoclave for reaction, and heating at 120 ℃ for 4 h. Cooling to room temperature, collecting samples, washing with deionized water for several times, and drying in a 70 ℃ oven for 8h to obtain composite materials with different vulcanization degrees, namely CuBi respectively2O4@CuBi2S4-1、CuBi2O4@CuBi2S4-2、CuBi2O4@CuBi2S4-3、CuBi2S4。
As can be seen from FIG. 1a, the composite material is a one-dimensional rod-like structure; further enlargement of the magnification (FIG. 1b) shows that the surface after vulcanization becomes rough, as in CuBi2O4The surface generates a lot of CuBi2S4The XRD spectrum of figure 2 confirms that the composite material is CuBi2O4@CuBi2S4。
Example 2 different gas Environment Pair H2O2Influence of generation
The method comprises the following steps: weighing one-dimensional rod-shaped CuBi2O4@CuBi2S450mg of the catalyst was added to a mixed solution containing 47.5mL of deionized water and 2.5mL of ethanol, and the mixture was sonicated for 10 min. Then using HClO4The pH of the suspension was adjusted to 3. Respectively adding N2Air and O2The suspension was passed through to allow continuous uniform bubbling through the solution. Magnetic stirring was then carried out in the dark for 30min to reach the adsorption-desorption equilibrium before irradiation. The mixture was irradiated with a 300W xenon lamp (. lamda. gtoreq.420 nm) as a light source to carry out the reaction. During the reaction, 1mL of suspension was extracted from the reaction cell every 30min, 2mL of 0.1mol/L KI solution and 0.05mL of 0.01mol/L ammonium molybdate solution were added, the absorbance A (detection wavelength: 350nm) was measured by UV-visible absorption spectrometry, and H was calculated from the established standard curve2O2The amount of production of (c).
When air is used in place of O2At ambient time, CuBi2S4@CuBi2O4H of (A) to (B)2O2Is reduced, which indicates that O is generated2Condition for photocatalysis H2O2Is facilitated. When using N2In place of O2At ambient time, no H2O2Production, indicated CuBi2S4@CuBi2O4Middle H2O2Is generated by O2By photoelectron reduction. And H cannot be detected without visible light radiation or photocatalyst2O2This indicates photocatalyst, visible light irradiation and O2Are all generating H2O2Are important factors of.
Example 3 pH vs H2O2Influence of generation
The method comprises the following steps: weighing one-dimensional rod-shaped CuBi2O4@CuBi2S450mg of the catalyst was added to a mixed solution containing 47.5mL of deionized water and 2.5mL of ethanol, and the mixture was sonicated for 10 min. Then using HClO4The pH values of the suspensions were adjusted to 1, 3 and 5, respectively. Then adding O2The suspension was passed through to allow continuous uniform bubbling through the solution. Magnetic stirring was then carried out in the dark for 30min to reach the adsorption-desorption equilibrium before irradiation. The mixture was irradiated with a 300W xenon lamp (. lamda. gtoreq.420 nm) as a light source to carry out the reaction. During the reaction, 1mL of suspension is extracted from the reaction tank every 30min, 2mL of 0.1mol/L KI solution and 0.05mL of 0.01mol/L ammonium molybdate solution are added, and purple treatment is carried outAbsorbance A (detection wavelength: 350nm) was measured by external-visible absorption spectrometry, and H was calculated from the established standard curve2O2The amount of production of (c).
When pH is 3, H within 120min2O2The amount of H produced was 164.3. mu. mol/L, and at pH 1, only 121.5. mu. mol/L of H was produced within 120min2O2This may be due to H being generated2O2Is gradually oxidized to H by excess protons2O(H2O2+2H++2e-=2H2O). When the pH was further increased to 5, H2O2The amount of production of (2) is reduced. The above results indicate that pH 3 is photocatalytic H production2O2The optimum pH value of (1).
EXAMPLE 4 one-dimensional rod-like CuBi2O4@CuBi2S4Preparation of H by catalysis of visible light catalyst2O2
CuBi is weighed respectively2O4、CuBi2O4@CuBi2S4-1、CuBi2O4@CuBi2S4-2、CuBi2O4@CuBi2S4-3 and CuBi2S450mg each was added to a mixed solution containing 47.5mL of deionized water and 2.5mL of ethanol, and sonicated for 10 min. Then using HClO4The pH of the suspensions was adjusted to 3, respectively. Then adding O2The suspension was passed through to allow continuous uniform bubbling through the solution. Magnetic stirring was then carried out in the dark for 30min to reach the adsorption-desorption equilibrium before irradiation. The mixture was irradiated with a 300W xenon lamp (. lamda. gtoreq.420 nm) as a light source to carry out the reaction. During the reaction, 1mL of suspension was extracted from the reaction cell every 30min, 2mL of 0.1mol/L KI solution and 0.05mL of 0.01mol/L ammonium molybdate solution were added, the absorbance A (detection wavelength: 350nm) was measured by UV-visible absorption spectrometry, and H was calculated from the established standard curve2O2The amount of production of (c).
Different proportions of photocatalyst H with increasing degree of sulfidation2O2The yield also gradually increases, and when the degree of vulcanization is further increased, H2O2Yield of (2) is rather decreased. After being irradiated by visible light for 180min, the CuBi with the optimal proportion2S4@CuBi2O4H of-22O2The yield reaches 201.9 mu mol/L and is CuBi alone2O4H of (A) to (B)2O21.7 times the amount produced.
Claims (9)
1. One-dimensional rod-shaped CuBi2O4@CuBi2S4The visible light catalyst is characterized in that the preparation method comprises the following steps: mixing Na2S is dissolved in water, CuBi is added2O4Stirring, transferring to a high-pressure kettle for reaction, cooling to room temperature, collecting a sample, washing, and drying to obtain a target product;
according to the mass ratio of CuBi2O4:Na2S is 5: 6.
2. the one-dimensional rod-like CuBi of claim 12O4@CuBi2S4The visible light photocatalyst is characterized in that the reaction is carried out by heating at 120 ℃ for 4 h.
3. The one-dimensional rod-like CuBi of claim 12O4@CuBi2S4The visible light catalyst is characterized in that the CuBi2O4The preparation method comprises the following steps: separately taking Bi (NO)3)3·5H2O、Cu(NO3)2·3H2Adding O and NaOH into deionized water, stirring, transferring into an autoclave for reaction, cooling to room temperature, collecting a sample, washing and drying to obtain CuBi2O4。
4. The one-dimensional rod-like CuBi according to claim 32O4@CuBi2S4The visible light catalyst is characterized in that Bi (NO) is added according to the mass ratio3)3·5H2O:Cu(NO3)2·3H2O:NaOH=242:60:87。
5. The one-dimensional rod-like CuBi according to claim 32O4@CuBi2S4The visible light photocatalyst is characterized in that the reaction is carried out by heating at 180 ℃ for 24 h.
6. The one-dimensional rod-like CuBi of claim 12O4@CuBi2S4The application of visible light catalyst in preparing hydrogen peroxide by photocatalysis.
7. Use according to claim 6, characterized in that the method is as follows: the one-dimensional rod-like CuBi of claim 12O4@CuBi2S4Adding visible light catalyst into deionized water, performing ultrasonic treatment for 10min, adjusting pH to acidity, and adding O2Introducing into the suspension, bubbling in the solution continuously and uniformly, magnetically stirring in dark for 60min to reach adsorption-desorption equilibrium before irradiation, and irradiating with light source for reaction.
8. Use according to claim 7, wherein the pH is adjusted by HClO4The pH of the suspension was adjusted to 3.
9. The application of claim 8, wherein the light source is a 300W xenon lamp with a lambda of 420nm or more.
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